CN1220673A - Durable, low surface energy compounds and articles, apparatuses, and methods for using the same - Google Patents
Durable, low surface energy compounds and articles, apparatuses, and methods for using the same Download PDFInfo
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- CN1220673A CN1220673A CN97195111A CN97195111A CN1220673A CN 1220673 A CN1220673 A CN 1220673A CN 97195111 A CN97195111 A CN 97195111A CN 97195111 A CN97195111 A CN 97195111A CN 1220673 A CN1220673 A CN 1220673A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C5/00—Apparatus in which liquid or other fluent material is projected, poured or allowed to flow on to the surface of the work
- B05C5/007—Slide-hopper coaters, i.e. apparatus in which the liquid or other fluent material flows freely on an inclined surface before contacting the work
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/42—Introducing metal atoms or metal-containing groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C9/00—Apparatus or plant for applying liquid or other fluent material to surfaces by means not covered by any preceding group, or in which the means of applying the liquid or other fluent material is not important
- B05C9/06—Apparatus or plant for applying liquid or other fluent material to surfaces by means not covered by any preceding group, or in which the means of applying the liquid or other fluent material is not important for applying two different liquids or other fluent materials, or the same liquid or other fluent material twice, to the same side of the work
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Abstract
Novel polymeric compounds having pendent fluoroaliphatic groups, pendent organic-solubilizing groups, and pendent groups capable of reacting with an epoxy silane; which have been reacted with an epoxy silane have been discovered. These compounds are easy to apply, abrasion and impact resistant, and provide durable, low surface energy, streak reducing surfaces on coating dies, edge guides, and other coating and fluid contacting surfaces.
Description
Invention field
The present invention relates to novel macromolecular compound and they as die head, fabric guide, and the application of other surperficial weather resistance low surface energy coats of apparatus for coating and other and fluid contact component.More particularly, the present invention relates to novel macromolecular compound and they share with the damage that will play the bar phenomenon and caused by the die cleaned operation with the coating die head and is reduced to a minimum.
Background of invention
It is known that liquid is applied the method that promptly is coated on the base material (thin slice).Yet this method can be very complicated, and this depends on used liquid and base material, and depend on performance objective and this method itself of the finished product.Developed many through the apparatus for coating that changes and coating process to satisfy special coating needs.
U.S. Patent No. 2,681,294 disclose a kind of vacuum method, can be used in coating fluid pearl (coating bead) stabilization of directly extruding with sliding type metering coating system.Such stabilization can improve the coating ability of these systems.Yet these coating systems lack the thin required enough integration capability of wet layer that some coated product requirement is provided, even under the low-down condition of liquid viscosity.
U.S. Patent No. 4,445,458 disclose a kind of extrusion type liquid pearl coating die head, and it has the skewed surface of leaving behind to apply boundary force in the downstream side that is coated with the feed liquid pearl and to reduce and keep the required vacuum capacity of liquid pearl.Noticed that reducing vacuum can make the line that quivers, striped and other coating defects reduce to minimum degree.And noticed with the obtuse angle of skewed surface and slit die axle with along oblique slit die axle and can further improve coating quality towards the thin slice that is moving (suspension) with away from the position optimizing of the thin slice that is moving (from lower support).Optimized result is to have obtained the required high quality of coating photosensitivity emulsion.But lack the required thin layer performance of some coated product.
The problem that extrusion die hair style coating machine and slip coating machine often run into is striped can occur when applicating liquid on base material.A reason that produces striped be near the liquid on the die lip that is coated with the feed liquid pearl do solid back residual due to.This reason and consequent stripes problem are especially general in the low-viscosity (mobile) liquid that contains the high volatile volatile solvent.
The open communique EP0581962A0 of european patent application has described a kind of scheme that reduces coating defects.This scheme is, the eutectoid dispersion of fluorine resin (as tetrafluoroethylene) and nickel is plated on the die surfaces and die lip of apparatus for coating.It is reported that after the curing, this surface has coating die head required hardness and dimensional stability and keeping the repellency of fluorinated surface simultaneously.Notice that this processing can prevent the applied liquid wets of die surfaces and rise bar, drop sagging and the edge that reduce in the coating process cross trace.
U.S. Patent No. 5,380,365 described with lower-energy material (as fluorinated polyethylene) cover (coating) near the liquid pearl or below slip be coated with the surface of die head.This tectum below coating die lip tip the 0.05-5.00mm beginning and from the coating fluid pearl to around extension.Separated by a metal strip that exposes between low surface energy tectum and the coating die head tip.This metal strip is positioned on the liquid pearl Static Contact line.Having noticed that the low energy tectum can be eliminated the coating striped and die head is cleaned becomes easy.
U.S. Patent No. 3,787,351 (Olson) etc. have described many known compounds.This patent has been described the oligopolymer that contains fluoro aliphatic group and polyoxyalkylene solubilizing group.These oligopolymer allegedly can be used as wetting agent to improve the mechanical property of potting resin mixture (as glass enhanced polyester or epoxy resin composite) molded article.And, U.S. Patent No. 4,415,615 (Esmay etc.) have described U.S. Patent No. 3,787, some oligopolymer of 351 as the application of tensio-active agent in preparation porous pressure sensitive adhesive to produce uniform vesicular structure.
The polymerisable surfactant of nonfluorinated has among 599 (Regen) and describes for example in U.S. Patent No. 4,560.This patent has been described the direct progressively method of applying solid base material of the polyfunctional polymerisable surfactant of a kind of usefulness.Used polymerisable surfactant is functional phosphatidylcholine of methacrylic ester and phosphoric acid ester.
Zh.Fiz.Khim., 1982,56,2898 (summaries) have been described a kind of formula CH
2=CHCO
2CH
2(CF
2CF
2)
nThe fluorinated acrylate of R (in the formula, R is H or F, and n is 1-4), this purposes that contains the oxypropylene acid esters are to make polymer surfaces produce hydrophobicity and chemical resistant properties by copolymerization.
U.S. Patent No. 5,468,812 (Muggli etc.) have described the high molecular oligomeric fluorine chemistry surfactant composition (being made by two functional monomers) with at least two fluoro aliphatic group side groups, at least two organic solubilized groups and a polymerizable thiazolinyl side group.These compositions can reduce with the acrylate surface energy of the pressure sensitive adhesive that is base.They can use in preparation with the acrylate is the pressure sensitive adhesive of base, because the existence of tensio-active agent, the gained tackiness agent can be coated with well and still can keep binder performance after aging.
Yet, still need a kind of wearing and tearing and/or ballistic material that can reduce striped that can stand generation under the normal running conditions.When the liquid of coating has abradability and when matting comprises with wipe surfaces such as cloth, brushes, wear resistance may particularly important.When coating process may occur comprising that thin slice is the situation of base material fracture and bump material, shock-resistance can particularly important.
The material that can reduce striped of weather resistance must be easily and apace and expense use cheaply.When administration of material, this application process should need not to make apparatus for coating off-line considerable time.Be preferably, application is very fast and can finish near coating position or its, and does not need apparatus for coating is contained on the equipment with hyperspecialization performance.
In addition, the application process of this minimizing streak material does not have and apparatus for coating is produced the remarkable danger of harmful effect.For example, need be warming up to apparatus for coating and produce the danger that makes the apparatus for coating size distortion more than the critical temperature thereby this method must not have.
The application process that reduces streak material also should only need medium initial cost, and method and material itself should be accomplished actual being applied in of material only needed average costs on the apparatus for coating.
Summary of the invention
The present invention is in order to overcome the shortcoming of known materials, specifically, to be provided at the surface that coating die head, fabric guide and other coating surfaces and the minimizing of other lip-deep weather resistance that contact with fluid play the bar phenomenon.An embodiment of the invention comprise novel macromolecular compound, and the compound of described novelty is a kind of fluorine chemistry oligopolymer, it comprise fluoro aliphatic group side group, organic solubilized group side group and can with the side group of epoxy-silane reaction.
In a preferred implementation, the fluorine chemistry of this polymkeric substance partly comprises an oligomeric aliphatic main chain, is connecting following groups on this main chain:
(ⅰ) has the fluoro aliphatic group of perfluorination end group;
(ⅱ) contain the organic solubilized group that many carbon atoms also can at random contain the Sauerstoffatom of one or more links;
(ⅲ) can with the organo-functional group of epoxy-silane reaction,
Each fluoro aliphatic group, organic solubilized group and can be connected independently by covalent linkage, heteroatoms or organic linking group with the group of epoxy-silane reaction on the oligomerization aliphatic series main chain.
In a preferred implementation, epoxy-silane contains epoxy-terminated and polymerisable silane end group.
In another preferred implementation, fluorine chemistry partly comprises the oligopolymer that one or more formula I are represented:
In the formula, R
1, R
2And R
3Represent the polymerized unit that obtains by fluorinated monomer, two functional monomers and solubilising monomer respectively and form aliphatic main chain jointly;
Each Q represents covalent linkage, heteroatoms or organic linking group independently;
Rf represents to contain the fluoro aliphatic group of perfluorination end group;
Rb represent can with the organo-functional group of epoxy-silane reaction;
Rs represents to contain the organic solubilized group that many carbon atoms also can at random contain the Sauerstoffatom of one or more links;
A, b, c and d are that to make this compound be the integer of oligopolymer;
Epoxy-silane is represented with following formula
With
In the formula, m and n are 1 to 4 integers; R is that carbon atom is at the aliphatic group below 10; Carbon atom is at the acyl group below 10; Or formula (CH
2CH
2O)
jThe group of Z (wherein, j is at least 1 integer); Z is that carbon atom is at the aliphatic group below 10.
In yet another preferred embodiment, fluorine chemistry partly comprises the oligopolymer that one or more formula II are represented:
In the formula, R
4Be hydrogen, halogen or methyl; The definition of Rf, Rs, Rb, a, b, c and d is the same.
The present invention also provides a kind of method for preparing above-mentioned composition, and it may further comprise the steps:
(ⅰ) with fluorinated monomer, have can with two functional monomers and the solubilising monomer oligomerization of the group of epoxy-silane reaction, form midbody composite;
(ⅱ) make the intermediate and the epoxy-silane reaction of step (ⅰ), to generate a kind of weather resistance low surface energy compounds.
Be used for herein representing that the chemical formula of oligomer structure of the present invention has shown that the unitary chain of the random polymerization that is obtained by a few class monomers exists; These chemical formulas are not to be used for representing unitary polymerization order, for example, and unitary " block " in segmented copolymer or unitary the replacing in chain.Herein, term " oligopolymer " or " oligomeric " are meant such compound, and it contains many polymerized units, but are less than the polymerized unit number of polymkeric substance, for example are 5 chains to about 100 polymerized units.
Discuss and some substituently quotes simplification for making, term " group " and " part " are used for distinguishing those can substituted chemical group and those chemical groups that is not replaced like this.Therefore, when term " group " or " acyl group " when being used for describing substituting group, this substituting group comprises other the substituent uses outside the literal definition of basic group.When term " part " when being used for describing substituting group, then only comprise the unsubstituted group of indication.For example, phrase " alkyl group " indication not only comprise pure hydro carbons alkyl chain (as methyl, ethyl, propyl group, the tertiary butyl, cyclohexyl, iso-octyl, octadecyl etc.), and comprise alkyl chain with substituting group known in the art (as hydroxyl, alkoxyl group, phenyl, halogen atom (F, Cl, Br and I), cyano group, nitro, amino, carboxyl etc.).For example, alkyl group comprises ether (for example, CH
3-CH
2-CH
2-O-CH
2-), haloalkyl, 4-nitro alkyl, carboxyalkyl, hydroxyalkyl, sulfo group alkyl etc.On the other hand, phrase " moieties " only comprises pure hydro carbons alkyl chain, as methyl, ethyl, propyl group, the tertiary butyl, cyclohexyl iso-octyl, octadecyl etc.Can be with the substituting group (as very strong Electron Affinities or oxidisability substituting group) of activeconstituents reaction because it is not an inertia or harmless and will be foreclosed by those of ordinary skill in the nature of things.
From below detailed description, embodiment and claims, can know and see other aspects of the present invention, advantage and benefit.
The simple description of drawing
Aforementioned advantages of the present invention, formation and utilization are easier to be clear that from following description and accompanying drawing.
Fig. 1 is the cross section side-looking synoptic diagram of extrusion die of the present invention;
Fig. 2 is the partial cross-sectional side view of extrusion die shown in Figure 1;
Fig. 3 is used in to apply the device of sandblasting is carried out on weather resistance low surface energy of the present invention surface before to the surface isogonism synoptic diagram;
Fig. 4 is the isogonism synoptic diagram that can be used for applying the device of weather resistance low surface energy top coat of the present invention;
Fig. 5 is the cross section side-looking synoptic diagram of slip apparatus for coating of the present invention;
Fig. 6 is the partial cross-sectional side view of slip apparatus for coating shown in Figure 5;
Fig. 7 is the partial cross-sectional side view of slip apparatus for coating shown in Figure 6;
Fig. 8 is the partial top view of slip apparatus for coating shown in Fig. 5-7.
Detailed description of the preferred embodiment
The macromolecular compound of novelty of the present invention especially can be used as die head, the guide of apparatus for coating and is coated with and arranges Durability low-surface-energy (DLSE) coating that other that put are surperficial. Disclose below preferred composition and goods, The using method of device and composition. And in connection with preferred embodiment shown in the formula I to fluoro aliphatic series of the present invention Fluorinated monomer, two functional monomers and the organic solubilized monomer of oligomer part further illustrate. The fluoro aliphatic monomers
Fluorinated monomer contains the fluoro aliphatic group, represents with Rf herein. Rf be stable, inertia with nonpolar, Be preferably not only oleophobic but also hydrophobic saturated univalent perssad. The fluorinated oligomeric thing preferably contains about 2-25 Rf base Group also preferably contains the fluorine atom of the about 5-30% (being preferably about 8-20%) that accounts for the oligomer gross weight, Fluorine atom is located substantially in the Rf group. Rf preferably contains at least 3 and (is preferably 3-20, preferably 6-12) carbon atom. Rf can contain straight chain, side chain or ring-type fluoro-alkyl or their combination, perhaps it With the combination of straight chain, side chain or cyclic alkyl. Rf does not preferably have polymerisable alkene unsaturated bond and can be any Ground contains the hetero atom of link, such as oxygen, divalence or sexavalence sulphur or nitrogen. Each Rf preferably contains about 40-78 weight The fluorine of % (being preferably about 50-78 % by weight). The end of Rf group contains the perfluorinate end group. This end group Preferably contain at least 7 fluorine atoms, for example CF3CF
2CF
2-、(CF
3)
2CF-etc. Perfluoroaliphatic group group's (that is, formula CyF
(2y-1)Those groups) be the most preferred example of Rf.
The fluoro aliphatic monomers is to fluoridize ethylenically unsaturated monomers. It is known fluoridizing ethylenically unsaturated monomers and preparation method thereof And be disclosed in for example U.S. Patent No. 2,803,615 (Ahlbrecht etc.) and 2,841,573 (Ahlbrecht Deng) in. The example of these compounds comprises all kinds of fluorine chemistry alkene, as contains the acrylic acid of fluoro sulfonamido group Ester, methacrylate, vinyl ethers and allyl compound, by fluorine chemistry telomer alcohol, fluorine chemistry mercaptan The acrylate that obtains or methacrylate etc.
In its simplest form, fluoridizing ethylenically unsaturated monomers, to contain the carbon that is connected on the alkene unsaturated group fluorine-based Group. Perhaps and be preferably, the carbon fluorin radical is connected on the hydrocarbon part, and the hydrocarbon part is connected on the alkene unsaturated group. The fluorine chemistry group can directly be connected on the hydrocarbyl group or it can connect by abutment (such as sulfonamido). Should The unsaturated part of preferred alkene of monomer is acrylate group or methacrylate based group. Preferred abutment is Sulfonamido.
It is representational that to fluoridize ethylenically unsaturated monomers as follows:
C
8F
17CH
2CH
2N(CH
3)C(O)CH=CH
2、
Ca
8F
17CH
2CH
2OC(O)CH=CH
2、
C
6F
13C
2H
4SC(O)CH=CH
2、
C
7F
15CH
2OC(O)C(CH
3)=CH
2、
C
8F
17SO
2N(C
2H
5)C
2H
4NHC(O)CH=CH
2、
(CF
3)
2CF(CH
2)
8C
2H
2SC(O)C(CH
3)=CH
2、
C
8F
17SO
2N(CH
3)C
2H
4OC(O)CH=CH
2、
C
8F
17SO
2N(CH
3)CH
2C
6H
4CH=CH
2、
C
6F
13CH
2CH
2O(O)CC(=CH
2)COOCH
2CH
2C
6F
13、
C
7F
15CH
2OOCCH=CHCOOCH
2C
7F
15、
C
6F
13C
2H
4N(CH
2CH
2OH)C(O)CH=CH
2、
C
7F
15CON(C
2H
5)C
3H
6SC(O)C(CH
3)=CH
2、
C
6F
13CH
2NHC(O)CH=CH
2、
C
8F
17CH
2CH
2OCH=CH
2、
(CF
3)
2CF(CF
2)
6CH
2CH(OH)CH
2OC(O)CH=CH
2、
(CH
3)
2CFOC
2F
4OC(O)CH=CH
2,
C
8F
17C
2H
4SO
2N(C
3H
7)C
2H
4OC(O)CH=CH
2、
C
7F
15C
2H
4CONHC
4H
8OC(O)CH=CH
2、
C
7F
15COOCH
2C(CH
3)
2CH
2OC(O)C(CH
3)=CH
2、
C
8F
17SO
2N(C
2H
5)C
4H
8OC(O)CH=CH
2、
(C
3F
7)
2C
6H
3SO
2N(CH
3)C
2H
4OC(O)CH=CH
2、
C
8F
17CF=CHCH
2N(CH
3)C
2H
4OC(O)CH=CH
2、
C
8F
17SO
2N(CH
3)CH
2CH
2OC(O)C(CH
3)=CH
2,
C
6F
13SO
2N(CH
3)CH
2CH
2OC(O)CH=CH
2
C
8F
17SO
2N(CH
3)CH
2CH
2OCH
2=CH
2、
C
8F
17SO
2NHCH
2CH=CH
2 
With their combination.Preferably fluoridize ethylenically unsaturated monomers vinylformic acid perfluor aliphatic series sulfonamido ester and their combination are arranged.Representational preferred vinylformic acid perfluor aliphatic series sulfonamido ester comprises:
C
8F
17SO
2N(C
2H
5)C
2H
4NHC(O)CH=CH
2、
C
8F
17SO
2N(CH
3)C
2H
4OC(O)CH=CH
2、
C
8F
17SO
2N(C
2H
5)C
2H
4OC(O)C(CH
3)=CH
2、
C
8F
17SO
2N(CH
3)CH
2C
6H
4CH=CH
2、
C
8F
17C
2H
4SO
2N(C
3H
7)C
2H
4OC(O)CH=CH
2、
C
8F
17SO
2N (C
2H
5) C
4H
8OC (O) CH=CH
2, and
(C
3F
7)
2C
6H
3SO
2N(CH
3)C
2H
4OC(O)CH=CH
2。The organic solubilized monomer
The organic solubilized monomer contains organic solubilizing group, represents with Rs herein.The Rs group dissolves in the organic medium (as solvent commonly used, the example of common solvent has the polymerizable mixture of ketone, ester, ether, hydrocarbon, vinylformic acid, methacrylic acid, acrylate and methacrylic ester etc.) the fluorinated oligomeric thing that makes in step (ⅰ).The especially preferred number of Rs group will depend on that concrete Rs group and compound intend the character of the concrete medium of solubilising therein.But usually, the number of Rs group is preferably for example about 2-60, is more preferably about 4-30.Each Rs group contains at least 4 carbon atoms and can at random contain the Sauerstoffatom of at least one link.The Rs group preferably contains about 8-50 carbon atom and can be straight chain, side chain, cyclic or their arbitrary combination.Organic solubilized radicals R s is the side group of fluorinated oligomeric thing preferably.Preferred Rs group comprises polyoxy alkylidene or polyoxyalkylenes (as polyoxyethylene or polyoxyethylene groups) and straight chain, side chain, cyclic alkyl or alkylidene group (as butyl, butylidene, octyl group, octylene, iso-octyl, inferior iso-octyl, octadecyl or inferior octadecyl) and their combination.
The solubilising monomer is known and generally is commercially available or those skilled in the art can easily be prepared.The monomeric example of solubilising comprises the C of vinylformic acid and methacrylic acid
2Above (is preferably C
4More than) alkyl ester, as Propenoic acid, 2-methyl, isobutyl ester, Isooctyl acrylate monomer, methacrylic acid stearyl etc.; The acrylate of polyalkylene glycol and methacrylic ester are as the triglycol acrylate; The acrylate of methoxy poly (ethylene glycol) and polyoxyethylene glycol and methacrylic ester, by the acrylate and the methacrylic ester of the acrylate of the segmented copolymer of hydroxy-end capped oxyethane and propylene oxide and methacrylic ester, erythritan; With amino is the acrylamide and the Methacrylamide of the polyethers of end group.Two functional monomers
Two functional monomers contain organic functional group and represent with Rb herein, it can with epoxy-silane reaction.Rb can be can with any group of epoxy-silane reaction.The example of these groups comprises hydroxyl, amino, carboxylic acid and sulfonic acid.Rb is hydroxyl preferably.Two functional monomers that contain these groups are known and generally are commercially available or those skilled in the art can easily be prepared.
Two functional monomers' example comprises: the hydroxyl C of acrylamide, Methacrylamide, maleinamide, maleimide, N-N-isopropylacrylamide, oxalic dialdehyde diacrylamine, N hydroxymethyl acrylamide, N-methylol MAAm, diacetone-acryloamide(DAA), diacetone isobutyramide, methylolation diacetone-acryloamide(DAA), methylolation diacetone isobutyramide, vinylformic acid 2-hydroxyl-3-chlorine propyl ester, methacrylic acid 2-hydroxyl-3-chlorine propyl ester, vinylformic acid and methacrylic acid
2-C
4Alkyl ester, iso-butylene glycol, allyloxyethanol, o-allyl phenol, divinyl methyl alcohol, glycerol α-allyl ethers, vinylformic acid, methacrylic acid and their metal-salt, vinyl sulfonic acid and vinylbenzene p-sulfonic acid and their metal-salt, 3-aminobutene nitrile, monoene propyl amides, 2-acrylamido-2-methyl propane sulfonic acid (AMPS) and salt, glycidyl acrylate and glycidyl methacrylate, glycidyl allyl ether and propenal.
Preferred two functional monomers are acrylate monomers of hydroxyl, as:
Hydroxyethyl methylacrylate (HEMA),
Hydroxyethyl acrylate (HEA),
Rocryl 410 and Propylene glycol monoacrylate.The fluorinated oligomeric thing
As mentioned above, the fluorinated oligomeric thing is following polymer of monomers: fluoridize ethylenically unsaturated monomers; The polyoxyethylene ethylenically unsaturated monomers; With two functional ethylenically unsaturated monomers.The example of unsaturated allyl compound comprises various types of olefins, as acrylate, methacrylic ester, vinyl ether and allylic cpd.The fluorinated oligomeric thing that can use in the present invention can be used U.S. Patent No. 5,468, and the method described in 812 is prepared.
Can easily prepare the fluorinated oligomeric thing, the high polymer main chain of required side functional group is arranged above producing thus.This preparation can easily be carried out by the following method: be chosen in the suitable ethylenically unsaturated monomers of pendant groups existing required on the monomer, like this, these pendant groups are also attached on the main polymer chain.This preparation is preferably by carrying out at least 3 kinds of material polymerizations formation acrylate backbone.Though acrylate is not spendable unique material, they are the preferred substances that form main chain.
The fluorinated oligomeric thing makes 3 kinds of material radical polymerizations with the required ratio of final product.Be preferably, each monomeric ratio is as follows in the polymkeric substance: about 30-50 weight % fluoridizes ethylenically unsaturated monomers; The polyoxyethylene unsaturated monomer of about 44-64 weight %; Ethylenically unsaturated monomers with the hydroxyl of about 6-16 weight %; Be more preferably, 3 kinds of monomeric ratios are respectively 34.5,54,11.5 weight %.Be aggregated in the solvent (as ethyl acetate, 2-butanone, ethanol, 2-propyl alcohol, acetone etc.) and carry out.
In the preferred implementation shown in the formula I, aliphatic main chain contains the polymerized unit that makes this compound become the required enough numbers of oligopolymer.Be preferably, main chain contains about 5-100 (being more preferably about 10-50, preferably about 20-40) polymerized unit.Single polymerized unit can contain the side group of 1 above kind.Yet polymerized unit is preferably obtained by following monomer: fluorinated monomer, and promptly those contain the monomer of fluoro aliphatic group; The solubilising monomer, promptly those contain the monomer of solubilizing group; Two functional monomers, promptly those contain can with the further monomer of the functional group of reaction of epoxy-silane.Unitary relative number of a few class polymerizations and absolute number preferably should be able to make in the compound the corresponding side group of several classes of preferred number in the oligopolymer.Therefore, with regard to the formula I, be preferably, a is about 2-80 (be more preferably and be about 5-45); B is about 1-60 (be more preferably and be about 2-30); C is about 2-70 (be more preferably and be about 4-55).
The number of the unitary mol ratio of a few class polymerizations and fluoro-containing group, solubilizing group and the polymerizable thiazolinyl determined thus is inequality in each oligopolymer of the present composition in the aliphatic series main chain.Therefore, this paper is according to doing general the description by the overall ratio of each polymerized unit that obtains in a few class monomers to composition of the present invention and oligopolymer, and this overall ratio mainly is that their used relative quantities are determined during by the preparation composition.Connect basic Q
In the fluorinated oligomeric thing, fluoro-containing group, solubilizing group with can with the group through type I of epoxy-silane reaction in be designated as Q the base that is connected be connected on the aliphatic main chain.Connecting basic Q can be covalent linkage, heteroatoms (as O or S) or organic group.Connect the organic group that basic Q preferably contains about 1-20 carbon atom, and can at random comprise the group that contains oxygen, nitrogen or sulphur or their combination, preferably do not have following functional group, obviously influence the functional group of free radical oligomerization as polymerisable alkene double bond, thiol group, easy bereft hydrogen atom (as cumyl hydrogen) and other meetings well known by persons skilled in the art.The example of structure that is fit to connect basic Q comprises straight chain, side chain or cyclic alkylidene, arylidene, inferior aralkyl, oxygen base, oxo base, thio group, alkylsulfonyl, sulfinyl, imino-, sulfonamido, formamido group, oxygen carbonyl, imino-formic acid ester group, ureylene and their combination (as the sulfonamido alkylidene group).Preferred connect basic Q can be whether easily and market on sale selection the whether according to preparation, and can whether Rf, Rs or Rb be connected on the aliphatic main chain and different according to it.
Be the representative table look-up of part of suitable organic Q group below.In this table look-up, each K represents the integer of about 1-20 independently, and g represents the integer of about 0-10, and h represents the integer of about 1-20, and R ＇ represents the alkyl of hydrogen, a phenyl or 1-4 carbon atom, the R " alkyl of representing about 1-20 carbon atom.
-SO
2NR＇(CH
2)
kO(O)C-
-CONR＇(CH
2)
kO(O)C-
-(CH
2)
kO(O)C-CH
2CH(OH)CH
2O(O)C-CH
2CH(OR″)CH
2O(O)C-
(CH
2)
kC(O)O-(CH
2)
kSC(O)-
-(CH
2)
kO(CH
2)
kO(O)C-
-(CH
2)
kS(CH
2)
kO(O)C-
-(CH
2)
k(OCH
2CH
2)
kO(O)C-
-(CH
2)
kSO
2(CH
2)
kO(O)C-
-SO
2NR＇(CH
2)
kO(CH
2CH
2)
kO(O)C-
-(CH
2)
kSO
2NR＇(CH
2)
kO(O)C-
-(CH
2)
kSO
2-
-SO
2NR＇(CH
2)
k-
-OC
6H
4CH
2O(O)C-
-(CH
2)
hO((O)C(CH
2)
6O)
gC(O)(CH
2)
6OC(O)-
-(CH
2)
hO((O)C(CH
2)
6NH)
gC(O)(CH
2)
6NHC(O)-
-C(O)O(CH
2)
2OC(O)NH(CH
2)
2OC(O)-
-(CH
2)
hO(CH
2CH-O)
g-CH
2CH
2-OC(O)-
-CH
2CH
2OC(O)-
-CH
2CH
2CH
2OC(O)-
For connecting Rf, Q is alkylidene group or sulfonamido or sulfonamido alkylidene group preferably.For connecting Rs, Q is the oxygen carbonyl preferably.For connecting Rb, Q is alkylidene group oxygen base carbonyl preferably.
The aliphatic main chain of fluoro aliphatic series oligopolymer does not exist with the form shown in the formula I certainly.Or rather, its each end is hydrogen or certain organic group (not expression in the formula I).End group is to exist owing to being used for preparation method for compositions.Concrete end group in the concrete fluorochemicals is not crucial for present composition function.Typical end group comprises hydrogen or alkylthio, and alkylthio can be obtained by the alkylthio chain-transfer agent.
Most preferred fluorinated oligomeric thing can be prepared shown in following reaction process:
In the step (ⅰ) of reaction process,, form the fluorinated oligomeric thing intermediate of formula II with fluorinated monomer, two functional monomers and solubilising monomer oligomerization.
In the fluorinated oligomeric thing of formula II, R
4, Q, Rf, Rs, Rb, a, b, c and d definition the same.Do not show in superincumbent chemical formula of the end group of oligomer chain or the reaction process.
In the step (ⅰ) of reaction process, there are a few class monomers of aequum, can produce all kinds of monomeric product that contains required relative number.Also have chain-transfer agent in step (ⅰ), it can play a part oligomer chain is terminated in suitable length, thus all kinds of monomeric absolute numbers in the control compound.Suitable chain-transfer agent contains and can increase and stop the group of free radical reaction and be known in those skilled in the art.Representational chain-transfer agent comprises mercaptan, as sulfur alcohol, propylmercaptan, butyl sulfhydryl, octyl mercaptan, uncle's dodecyl mercaptans, 2-sulfydryl ether, 2-sulfydryl-imidazoles etc.Chain transfer dosage in step (ⅰ) must be enough to control the number of polymerized unit in the aliphatic main chain.About 1-20% of monomer molar number during the consumption of chain-transfer agent generally is equivalent to react is preferably and is about 3-10%.
In step (ⅰ), also there is radical initiator.These compounds are that those skilled in the art are known, comprise persulphate, azo-compound (as Diisopropyl azodicarboxylate and azo-2-cyanopentanoic acid etc.), hydroperoxide (as cumene hydroperoxide, tertbutyl peroxide, t-amyl peroxy hydrogen), dialkyl peroxide (as ditertiary butyl peroxide), peracid ester (as t-butylperoxyl benzoate and peroxide phthalic acid di tert butyl carbonate), diacyl peroxide (as benzoyl peroxide and lauroyl peroxide).
The appropriate amount of initiator depends on used concrete initiator and other reactants.Can use the initiator of about 0.1-5% (being preferably about 0.1-1%) of other all reactant gross weights in being equivalent to react.
Step (ⅰ) is preferably in the inert atmosphere (for example in the exsiccant nitrogen atmosphere) carries out.Step (ⅰ) can be carried out in the solvent of any suitable organic free radical reaction.Reactant can be present in the solvent and any suitable concentration, for example accounts for about 5-90% of reaction mixture gross weight.The example of suitable solvent comprises aliphatic series and clicyclic hydrocarbon, as hexane, heptane and hexanaphthene; Aromatic solvent is as benzene, toluene and dimethylbenzene; Ether is as ether, glycol dimethyl ether, diglyme and Di Iso Propyl Ether; Ester is as ethyl acetate and butylacetate; Ketone is as acetone, methyl ethyl ketone (MEK, 2-butanone) and methyl iso-butyl ketone (MIBK); Sulfoxide is as dimethyl sulfoxide (DMSO); Acid amides, as N, dinethylformamide and N,N-dimethylacetamide; Halogenated solvent is as trichloroethane, Freon 13 (Freon 13), trieline and α, α, α-phenylfluoroform etc. and their mixture.
Similarly, step (ⅰ) can be carried out under the temperature of any suitable organic free radical reaction.Used actual temp and solvent can be easily selected on the basis of having considered related factors (as the solvability of reagent, concrete initiator required use temperature etc.) by those skilled in the art.Do not have practical significance though enumerate the actual temp that is fit to all initiators and all solvents, generally speaking, suitable temp is between about 30-200 ℃.
Should understand, prepare the other method that contains the fluorinated oligomeric compositions (as crosslinked composition) of the solubilizing group of link of the present invention be included in use in the step (ⅰ) two functional solubilising monomers (that is the monomer that, contains the solubilizing group that two polymerizable olefins are partly connected) rather than above enumerate the solubilising monomer of the simple function of explanation.The suitable monomeric example of two sense solubilisings comprises the diacrylate and two (methacrylic ester) of poly-alkane glycol such as Carbowax 1000,1450 and 3350.When using two such sense solubilising monomers, step (ⅰ) produces the slight crosslinked fluorinated oligomeric thing of the solubilizing group that contains link.According to the character of Rs group, the product of step that can this is other (ⅰ) transforms promptly as mentioned above integrating step (ⅱ) and carries out further syntheticly, produces composition of the present invention.Epoxy-silane
As mentioned above, in step (ⅱ), fluorinated oligomeric thing and the further polymerization of epoxy-silane with the formula II form weather resistance low surface energy of the present invention (DLSE) coating.
Epoxy-silane is that the compound with polymerizable (being preferably end group) epoxy group(ing) and polymerizable silane end group is a material, but aliphatic series, the aromatics of these groups by non-hydrolysable connects base or the aliphatic series by nitrogen atom on the connection chain and/or Sauerstoffatom is connected with the aromatics divalent linker.Sauerstoffatom in chain for example only as ehter bond.
Preferred epoxy-the silane that can use in radiation curable compositions of the present invention is the compound that has polymerizable epoxy base (Oxyranyle) and silylation at two ends respectively, can be represented by the formula:
With
In the formula, n is the integer of 1-4; R is that carbon atom is at the aliphatic group below 10, as methyl, ethyl, sec.-propyl, butyl, vinyl, allyl group; Or carbon atom is at any acyl group below 10, as formyl radical, ethanoyl or propionyl; Or formula (CH
2CH
2O)
jAny group of Z, wherein j is at least 1 integer; Z is that carbon atom is at any aliphatic group below 10, as methyl, ethyl, sec.-propyl, butyl, vinyl and allyl group.Be preferably, R is the alkyl of 1-3 carbon atom.The example of representational preferred epoxy-silane comprises:
γ-Huan Yangbingyangbingjisanjiayangjiguiwan,
γ-epoxypropoxy triethoxyl silane,
γ-epoxy third oxygen ethyl trimethoxy silane,
γ-(3, the 4-epoxycyclohexyl) propyl trimethoxy silicane,
γ-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, or the like.Most preferred epoxy-silane compound is a γ-Huan Yangbingyangbingjisanjiayangjiguiwan.
Except that above-mentioned epoxy-silane, composition of the present invention can be any hydrolysate, prepolymer or the precondensate of above-mentioned silane.Hydrolysate can by with the OR group of silane partially or completely hydrolysis form.Thereby " precondensate " speech comprises that some Siliciumatoms wherein pass through Sauerstoffatom and the siloxanes of bonding.Prepolymer is by U.S. Patent No. 4,100, and the prepolymerization of the group beyond the 134 described silane forms.
Polymerisable epoxy functionalized silane accounts for the 76-95% of composition total weight, is preferably to account for 80-90%.The formation of weather resistance low surface energy polymeric
There are many catalyst systems to can be used for the preparation of coating of the present invention.In the curing system with epoxy group(ing) and polymerisable silane end group, those skilled in the art recognizes the effectiveness of many inhomogeneity catalyzer, and some catalyzer wherein both can make epoxy group(ing) solidify, and silylation is solidified.U.S. Patent No. 4,049,861 reports, height in hand fluorizated aliphatic series alkylsulfonyl and sulfonic acid catalyzes chaste tree are cured epoxy-silane.U.S. Patent No. 3,955,035 report, available Lewis acid and Bronsted acid catalyst are cured epoxy-silane, and U.S. Patent No. 4,101,513 reports, available " class " radiosensitive catalyzer is cured epoxy-silane.All these three classes catalyzer can make epoxy group(ing) and silylation be cured to different degree and be the preferred catalyzer of epoxy-silane.Can add different catalyzer (for example diazonium salt is useful) and be used for the other catalyzer of independent group, use with these catalyst combination.
The example that can be used for preparing representational useful " class " catalyzer of coating of the present invention is disclosed in United States Patent (USP) 4,156, in 046.Usually, they are " aryl class " catalyzer.
Example with cationic these catalyzer of periodic table of elements VII A family comprises:
Iodate Er Ben Ji Iodonium,
Chlorinated diphenyl Ji Iodonium,
Sulfuric acid Er Ben Ji Iodonium,
Trichoroacetic acid(TCA) Er Ben Ji Iodonium,
Diphenyl antimony chloride base bromine,
Iodate (4-chloro-phenyl-) Ben Ji Iodonium,
Chlorination two (4-p-methoxy-phenyl) Iodonium,
Tetrafluoroboric acid (4-aminomethyl phenyl) Ben Ji Iodonium,
Tetrafluoroboric acid (4-trifluoromethyl) Ben Ji Iodonium,
Phosphofluoric acid 2,2-phenylbenzene iodine,
Chlorination 1-(2-ethoxycarbonyl naphthyl) Ben Ji Iodonium.
Example with cationic these catalyzer of periodic table of elements V A family comprises:
Chlorination (4-acetyl phenyl) triphenyl ammonium,
Phosphofluoric acid (4-bromophenyl) triphenyl phosphonium,
Tetrafluoroboric acid two (1-naphthyl) Dimethyl Ammonium,
Phosphofluoric acid dibenzoyl methyl dimethoxy base ammonium,
Tetrafluoroboric acid diphenyl methyl ammonium,
Iodate four (4-chloro-phenyl-) Phosphonium,
Tetraphenylarsonium chloride base bismuth,
The iodate tetraphenylphosphoniphenolate,
The phosphofluoric acid tetraphenylphosphoniphenolate,
Tetrafluoroboric acid Si Ben Ji Arsenic and
Tetrafluoroboric acid three (3-thienyl) ammonium methyl.
Preferred " class " catalyzer of one class is to have the cationic catalyzer of periodic table of elements VI A family.The example of these catalyzer comprises:
The acetate triphenylsulfonium,
The hexafluoro-antimonic acid triphenylsulfonium,
The iodate triphenylsulfonium,
The sulfuric acid triphenylsulfonium,
The trichoroacetic acid(TCA) triphenylsulfonium,
Tetrafluoroboric acid (4-chloro-phenyl-) phenylbenzene sulfonium,
Iodate (4-cyano-phenyl) phenylbenzene sulfonium,
Sulfuric acid (2-nitrophenyl) phenyl methyl sulfonium,
The hexafluoro-antimonic acid triphenyl
, and
Pentachloro-bismuthic acid triphenyl tellurium.
Use the goods of the present composition and the using method of device
Fig. 1 and Fig. 2 are embodiment of apparatus for coating, and in this embodiment, extrusion die 10 is mutually opposed with pad roller 12.As shown in the figure, extrusion die 10 comprises the die holder 16 that die head top 14 and available for example 15-5 stainless steel are made.Die head inlet 18, die head aggregate pipe 20 and die orifice seam 22 are formed between die head top 14 and the die holder 16.
Liquid 24 (as solution, mixed solution, dispersion liquid or emulsion) available pump 26 (or other modes) supplies to die head 10 for being applied on the base material (thin slice) 28.Liquid 24 can enter the mouth by die head and 18 flow to die head aggregate pipe 20 for carrying out refining by die orifice seam 22.After flowing through die orifice seam 22 as shown in Figure 2, the liquid pearl of liquid 24 is applied on the thin slice 28, for example when thin slice is transferred between pad roller 12 and the die head 10.Vacuum chamber 29 can be applied to vacuum the upstream of liquid 24 of liquid pearl so that liquid pearl stabilization.
The die lip 30 of upstream and the die lip 32 in downstream can form sharp keen edge, or can be slicker and more sly, for example polish.The die lip 30 of upstream and the die lip 32 in downstream must be bright and clean, do not have breach and burr basically.
The key component of die head 10 can be strengthened with weather resistance low surface energy surface 50 (to call DLSE surface 50 in the following text).Compare with the stainless steel parts that die head 10 exposes, the surface energy on DLSE surface 50 is obviously lower, and the degree that is got wet by liquid 24 in DLSE surface 50 is reduced to minimum, thereby has reduced the formation of striped in the coating process.And contingent wearing and tearing and ballistic while in standing use, DLSE surface 50 provides this ability serially.In addition, the method for the die head 10 with DLSE surface 50 is provided is better simply and expense is cheap.
An embodiment on DLSE surface 50 can comprise above-mentioned weather resistance low surface energy composition and the adhesive ground coating composition that is used to improve to die head 10.The embodiment of these compositions has description in the embodiment of this specification sheets part.Can use the ground coating composition except that described in the embodiment part those.
Also can use the weather resistance low surface energy composition except that the embodiment part is described through changing.For example, the fluorine chemistry described in the embodiment can account for the 1-30 weight % of weather resistance low surface energy composition, is preferably and accounts for 5-20 weight %, is more preferably to account for 7-13 weight % (embodiment 1:10 weight %).
What Fig. 2 showed is, DLSE surface 50 can be embedded on the adjacent part of the adjacent part of die lip die head top 14 and the downstream 32 and die lip die holder 16 and the upstream 30.For inlaying DLSE surface 50, can on die head 10, punch out recess, fill up with ground coating composition and weather resistance low surface energy composition then.Inlaying the degree of depth can be for example between the 0.01-0.2500mm, but also can be deeply some or more shallow.Inlaying width can be for example between 1-250mm, but also can be narrower or wideer.It is preferably identical with die width to inlay length.
Die holder 16 and/or die head top 14 can be die-cut into DLSE surface 50 is set into as shown in the figure, in the position after a while of die lip.This method is to produce little shoulder on die lip.Perhaps, die holder 16 and/or die head top 14 can be die-cut into DLSE surface 50 is applied directly on the die lip.If this method of use, then the most handy mild abrasives rubbing down die lip makes its smooth surface.Another kind of selectable method is to apply DLSE surface 50 outside die lip with in the die orifice seam 22.Also having a kind of selectable method is only to apply DLSE surface 50 and do not punch out and inlay the required degree of depth in DLSE surface 50 on die holder 16 and/or die head top 14.
An embodiment in the method that applies the DLSE surface on the die head 10 has description in the embodiment of this specification sheets part.This method generally can may further comprise the steps: the specific part of (a) making the die head 10 be used to inlay DLSE surface 50, (b) with ground coating composition the part of making is carried out primary coat, (c) ground coating composition is solidified, (d) the solidified ground coating composition is done rough, (e) part toward primary coat applies weather resistance low surface energy composition, (f) weather resistance low surface energy component is solidified.
Manufacturing step can reach one or two purpose: at first, die head 10 and ground coating composition are adhered to better, secondly, punch out a recess that can apply silane coupling agent and weather resistance low surface energy composition.For protection DLSE surface 50, can cut a recess (groove) in the part that will apply DLSE surface 50 of die head.For better adhesion, the part that will apply DLSE surface 50 of die head can be done rough.Doing rough method has manyly, comprises sandblasting, with the manual polishing of fine sandpaper with use the strong acid chemical etching.Fig. 3 is the sandblasting device made from commercially available parts 60.This sandblasting device 60 can be injected in abrasive powder on the die head 10, and the required part surface of die head 10 is done rough.Sandblasting device 60 can comprise the device (not shown) of sand spraying device outer cover (not shown), air compressor or compressed nitrogen source of the gas (not shown), air or nitrogen pressure controller (not shown), abrasive particle hopper (not shown), conduit 62, nozzle 64, rotary nozzle and the device (not shown) of travelling workpiece.
Outer cover and hopper are the PROFINISH PF-3696 types that Pennsylvania Langhorne city Empire Abrasive Equipment company produces.Controller, conduit 62, nozzle 64 and abrasive particle powder are buied from California Burband city COMCO company.Preferred nozzle arrangement comprises two nozzles placed side by side.Preferred nozzle is COMCO MB 1500-23 type nozzle (rectangular apertures, 3.8mm * 0.02mm).The device that rotates (swing) nozzle comprises S57-83-MO type step motor and the S6 type driving mechanism that Rohnert Park city, California Compumotor branch office of Parker Hannifin company produces.
COMCO produces various MicoBlaster Precision abrasive powders, as Silicon Carbide (silicon carbide) powder and Alnminum Oxide (aluminum oxide) powder.For die head 10 mills that will make with the 15-5 stainless steel will be rough, preferably use the Silicon Carbide powder of particle diameter as the 10-100 micron, but also can use other particle diameters with other abrasive powders.
Pressurized air or nitrogen promote abrasive particle by conduit 62 and from nozzle 64 ejections.Nozzle 64 can point to workpiece (as die holder 16 (or die head top 14)), and like this, part 66 abrasions also will be clashed in the surface of abrasive particle bump die holder 16.Die holder 16 can be sheltered with adhesive tape, and like this, only the required part of die holder 16 is clashed into by abrasive particle.
For producing required abrasion part 66, air pressure preferably is made as 100 pounds/in2; The aperture of nozzle 62 preferably is located at the position from die holder 16 about 1.25cm; Nozzle promptly moves around with the speed of 2.5cm/min translational motion and rotate with 24 revolutions per seconds speed on die holder 16.Nozzle rotates in the scope of 26 degree or swing (spending with level+13 degree from become-13 with level).Nozzle is with speed translational motion on part of the die head of 2.5cm/min.But having shown, other speed, distance and scope can produce abrasion part 66 equally.(also can use other abrasion methods, comprise and use sand paper or other to do rough material).
Primary coat step (being particularly useful when applying DLSE surface 50 on parts of stainless steel) can comprise to be set level die head 10 and applies ground coating composition in the abrasion part 66 of die head 10.The prescription of ground coating composition has description in the embodiment part, but also can use this prescription or other prescriptions through changing.Though can or be injected on the part or a few part of die head 10 the ground coating composition brushing, Fig. 4 is the synoptic diagram of a preferred primary coat method.This method may further comprise the steps: (a) the abrasion part 66 with die holder 16 (or die head top 14) is placed on the opposite of composition applicator 70 and makes abrasion part 66 be in level, (b) with the composition applicator with control speed with respect to die holder 16 translations, (c) control is applied to the volumetric rate of the ground coating composition of die holder 16 from composition applicator 70, (d) with the ground coating composition spread-coating on the abrasion part 66 of die holder 16.
After being applied to ground coating composition on the abrasion part 66, make its curing with the ultraviolet light irradiation ground coating composition.The UV radiation source that Woburn city, Massachusetts XENON company produces can make the ultraviolet radiation pipe produce the pulse of certain frequency of certain hour.With regard to the ground coating composition of the abrasion part 66 that is applied to wide 12.5mm described in the embodiment part, the ultraviolet radiation pipe preferably places 0.5-5cm place, ground coating composition top, and the best frequency of pulse of generation is 7 times/second, and the time is 5-60 kind second.Preferred ultraviolet light pipe is the 890-1741 type, and its energy output is about 209 joules, is XENON company product.
After being solidificated in ground coating composition on the die holder 16, preferably sandblasting is carried out with the surface of improving primary coat and the tackiness between the weather resistance low surface energy composition (to call the DLSE composition in the following text) in the surface of primary coat, can use and foregoing same nozzle 64, but abrasive material is Silicon Carbide powder (particle diameter: 20 microns, COMCO company product).Be preferably, air pressure is 70 pounds/inch
2The aperture of nozzle 64 and the distance between the workpiece are 25.4mm; The slewing rate of nozzle 64 is 24 revolutions per seconds; Nozzle is 15.2cm/min in the speed of part of the die head front translation.
Then, available set compound applicator 70 is applied to abrasive on the surface of primary coat with the DLSE composition, and the step of back is identical with the step that the front applies ground coating composition.(also available additive method applies silane coupling agent and DLSE composition: use electrostatic sprayer, only be to use dropper, brush, even parts are immersed in the composition).Then, available aforementioned curing apparatus is cured weather resistance low surface energy composition.The application time of the ultraviolet radiation of chopping is preferably 18 seconds kinds.
After being solidificated in the DLSE composition on the die head top 14, final step can comprise with 50 polishings of the surface of the DLSE on die lip 32 tips in downstream, to eliminate or to reduce coarse (the coarse of tip may be caused by the sandblasting step) of tip.But this step only is suggestive, if applied the words of DLSE composition just on the tip of die lip 32.
Method on the aforesaid part that DLSE surface 50 is applied to die holder 16 and/or die head top 14 and the method that fluorinated polyethylene coating (for example polytetrafluoroethylene (PTFE)) is applied on the die head part can be compared.In the embodiment of this specification sheets part, comparative example has been described such PTFE method.PTFE coating and method and DLSE coating and method are significantly different aspect several.At first, though can be with PTFE coating abrasion to a certain degree and still providing the low surface energy surface, the PTFE coating is softer and when thin slice galled in the course of processing and clashes into the PTFE coating with enough power, it is useless that the PTFE coating can become.The DLSE coating then is not subject to the influence of this collision significantly.
Secondly, the method that applies PTFE is time-consuming more than the DLSE method.This is very important, because manufacturers always does one's utmost to shorten the stoppage time in the production process, for example, does one's utmost to shorten the coating of part of the die head or is coated with the time again.General estimation, applying PTFE composition required time is the manyfold that applies DLSE composition required time.This may produce the production program, production efficiency and initial cost and seriously influence very much.
In addition, in the PTFE method, need the die head part is handled under than the obviously high temperature of DLSE method.Be the PTFE coating on the roasting die head part, the die head part is placed baking oven and heat at about 575 °F (302 ℃).The DLSE method can comprise the die head part and to heat but be more preferably at about 110 °F (43 ℃) at about 80-140 °F (about 27-49 ℃).When the steel that will be used for making these die head parts is heated to 575 °F and when being cooled to room temperature again, must to prevent the die head part dimensional change and distortion appear by SC.This may be vital, because the surface of these die head parts generally is being coated with so that energy when die head uses is accurate of finish grinding, and dimensional change can make the die head part become useless.
And manufacturing PTFE coating comprises more step (for example, the last polishing of multilayer PTFE layer, PTFE coating) and need more handle the die head part of processing.The danger that the critical surface that more processing can increase the die head part clashes into another object unintentionally and sustains damage thus.Damage to the important surface of die head part can cause and need grind again the surface, and perhaps worse is to need impaired die head part is all changed.Natch, these results all can cause the further prolongation of stoppage time in the manufacturing processed and the remarkable increase of expenditure.
Fig. 5 is an embodiment of slip apparatus for coating 80, and it comprises the DLSE surface 50 on device 80 and two parts that liquid 24 contacts.Slip apparatus for coating 80 comprises slide assemblies 82 and sliding mats roller 84.Slide assemblies 82 comprises many slide blocks 86,88,90,92,94 that can simultaneously multilayer liquid 24 be transported on the thin slice 28.
Fig. 6-8 has more specifically shown the position of DLSE surface 50 on slip apparatus for coating 80.Specifically, what Fig. 6-7 showed is, DLSE surface 50 can be applied on the end face of last piece slide block 94 so that end face is wandered the degree that the liquid 24 on slip apparatus for coating 80 gets wet and be reduced to minimum.
Fig. 6 is the fabric guide 96 that is provided with liquid 24 guiding pad rollers 84 and thin slice 28.DLSE surface 50 can be applied on the part of fabric guide 96, thereby the degree of the fabric guide 96 of liquid 24 can being got wet is reduced to minimum.If fabric guide makes with stainless steel, then should be as previously described, do fabric guide rough and carry out primary coat.If but make with plastics (for example SL5170 Resins, epoxy of Ceiba-Geigy company), then can apply the DLSE composition and need not to do rough and the primary coat step.DLSE surface 50 is reduced to minimum in the degree that fabric guide and existence on the part that contacts of coating fluid are got wet fabric guide or its part.This existence can produce dysgenic coating solid gathering on fabric guide coating quality/do reducing to minimum degree admittedly.
Fig. 8 is the surface of first slide block 86 adjacent with pad roller 84.This surface can comprise DLSE surface 50 and is reduced to minimum so that the degree that the liquid 24 above it gets wet drops on these first slide block, 86 surfaces.And this gathers the coating solid and relevant bad result is reduced to minimum level.
Below in conjunction with embodiment objects and advantages of the present invention are illustrated, but concrete material that adopts among these embodiment and consumption thereof and other conditions and details should not be considered to limitation of the invention inadequately.
Embodiment
The all material of Shi Yonging all can obtain from the commercial channel (as state of Wisconsin Milwaukee city Aldrich Chemical company) that the source of goods can be provided at any time easily in the following embodiments.All per-cents all by weight, except as otherwise noted.In addition, more following terms and material have been used.
EtFOSEMA is meant methacrylic acid N-ethyl-perfluor (octane) sulfonamido ethyl ester, buys from Minnesota State St.Paul city 3M company.
γ-Huan Yangbingyangbingjisanjiayangjiguiwan is buied from Michigan State Midland city Dow Chemical company, and its ProductName is Z-6040.It also can be buied from Connecticut State Danbury city OSi Specialties company, and its ProductName is A-187.
The hexafluoro-antimonic acid triphenylsulfonium obtains from Minnesota State St.Paul city 3M company.It also can be buied from Connecticut State Danbury city Union Carbide company.Embodiment 1
The preparation of Carbowax 750 acrylate:
Carbowax 750 is poly glycol monomethyl ethers that Danbury city, Connecticut State Union Carbide company produces.It is believed that its molecular formula is about CH
3O (CH
2CH
2O)
16-OH.
Carbowax 750 acrylate are Carbowax 750 and acrylic acid reaction product.The preparation of Carbowax 750 acrylate has narration in U.S. Patent No. 3,787 among the embodiment 2 of 351 (Olson).
The preparation of fluorine chemistry oligopolymer: the preparation of fluorine chemistry oligopolymer is undertaken by embodiment 1 described method in the A part of U.S. Patent No. 5,468,812.
In the bottle of about 950ml, put into 75.0g (0.120 mole) methacrylic acid N-ethyl-perfluor (octane) sulfonamido ethyl ester, 117.5g (0.146 mole) Carbowax 750 acrylate, 25.0g (0.216 mole) Hydroxyethyl acrylate, 250g ethyl acetate solvent, 5.0g (0.034 mole) octyl mercaptan and 0.625g Diisopropyl azodicarboxylate.Decompression is down with the material degassing in bottle and the bottle, and is tight with nitrogen purging, lid, then in Launder-O-meter (washable tester) in 65 ℃ of heated and stirred 16 hours, obtain the fluorine chemistry oligopolymer.The bottle cooling is also under reduced pressure outgased, uses air purge, be used for next step then.The gained ethyl acetate solution contains the oligopolymer of 48 weight %.This oligopolymer contains 34.5% fluoro aliphatic monomers, 54.0% organic solubilized monomer and 11.5% 2 functional monomer.
The preparation of weather resistance low surface energy polymeric: the preparation method of weather resistance low surface energy polymeric is that following ingredients is mixed:
20.8g the 48 weight % solution of above-mentioned fluorine chemistry oligopolymer in ethyl acetate,
76.67g γ-Huan Yangbingyangbingjisanjiayangjiguiwan,
13.33g 30% hexafluoro-antimonic acid triphenylsulfonium in γ-Huan Yangbingyangbingjisanjiayangjiguiwan.
In this prescription, the fluorine chemistry oligopolymer accounts for 10 weight %, and the hexafluoro-antimonic acid triphenylsulfonium accounts for 4 weight %, and γ-Huan Yangbingyangbingjisanjiayangjiguiwan (Z-6040) accounts for 86 weight %.
The preparation of ground coating composition: the preparation method of ground coating composition is that following ingredients is mixed:
Glycerol propoxy-triacrylate (Ebecryl 53, Radcure company product)=53.8 weight %,
1,6 hexanediol diacrylate (SR 238, Sartomer Resins company product)=33.1 weight %,
Dipentaerythritol hydroxyl five acrylate (SR 399, Sartomer Resins company product)=5.5 weight %,
Irgacure 184 (1-hydroxycyclohexylphenylketone, Ciba-Geigy company product)=7.6 weight %.
Primary coat chaste tree and DLSE polymkeric substance applying on the coating die head: will shelter respectively with similar extrusion die top 12 and die holder 16 shown in Fig. 1-3, and only make those need abrasive part of the die head part (representing with DLSE surface 50 among the figure) to expose.Before this step, on die holder 16, cut recess so that inlay on DLSE surface 50; Recess is not cut at 14 at die head top.Shelter finish after, be about to part of the die head and insert respectively in the aforementioned sandblasting device 60, denude with the Silicon Carbide powder of 50 microns of particle diameters.Gas (nitrogen) pressure is made as 100 pounds/inch
2(6.89 * 10
2KPa); The aperture of nozzle 62 is located at from die holder 16 about 1.25cm places; Nozzle rotates with the speed moving linearly of 2.5cm/min and with 24 rev/mins speed on part of the die head and promptly moves around.
With aforementioned ground coating composition the abrasive part of the die head is carried out primary coat then.Fig. 4 is the synoptic diagram of preferred primary coat method.This method may further comprise the steps: (a) the abrasion part 66 with die holder 16 (or die head top 14) is placed on the opposite of composition applicator 70 and makes abrasion part 66 be in level, (b) with the composition applicator with control speed with respect to die holder 16 translations, (c) control is applied to the volumetric rate of the ground coating composition of die holder 16 from composition applicator 70, (d) with the ground coating composition spread-coating on the abrasion part 66 of die holder 16.Composition applicator 70 comprises pin 72, syringe 74 and with the transmission mechanism 76 of the speed push injection device of control.In the time of on ground coating composition being applied to the abrasion part 66 that about 12.5mm is wide, 0.08mm is dark, ground coating composition is with 7.0cm
3The speed of/hr applies and applicator 70 best speed translations with 15.2cm/min.With ground coating composition along the length of abrasion part 66 apply finish after, will touch seat and 16 leave standstill the regular hour, make ground coating composition to around flow and cover abrasion part 66.Available little painting brush that leaves a little bristle with the ground coating composition spread-coating to the All Ranges that is not covered by ground coating composition.
After being applied to ground coating composition on the abrasion part 66, ground coating composition is carried out ultraviolet radiation, make its curing with aforementioned XENON (UV radiation source).The ultraviolet radiation pipe places 1.6cm place, ground coating composition top, and the best frequency of pulse of generation is 10 times/second, and the time is 60 seconds kinds.
After being solidificated in ground coating composition on the die holder 16, using with the surface of 64 pairs of primary coats of foregoing same nozzle and carry out sandblasting, but use is Silicon Carbide powder (particle diameter: 20 microns).Gas (nitrogen) pressure is 70 pounds/inch
2(4.83 * 10
2KPa); The aperture of nozzle 64 and the distance between the workpiece are 25.4mm; The slewing rate of nozzle 64 is 24 revolutions per seconds; The nozzle moving linearly, and make speed on die holder 16 translation of nozzle materials flow with 15.2cm/min.
Then, available set compound applicator 70 is applied to abrasive on the surface of primary coat with aforementioned DLSE composition, and the step of back is identical with the step that the front applies ground coating composition, is preferably 5cm but apply speed
3/ hr.
Available aforementioned curing apparatus is cured the DLSE composition.The application time of the ultraviolet radiation of chopping is 18 seconds kinds.After being solidificated in the DLSE composition on the die head top 14, with the die lip 32 tips polishing in downstream, to eliminate or to reduce coarse (the coarse of tip may be caused by the sandblasting step) of tip.In this step, should be noted that so that 50 abrasions of DLSE surface are reduced to a minimum.
The method of these compositions and this manufacturing extrusion die provides low surface energy for processed surface.DLSE surface 50 and water, the aqueous solution of 6.4%MEK and the contact angle of 100%MEK are measured, and the result is respectively 100.1 degree, 69.2 degree and 43.6 degree.In use, observe DLSE surface 50 and can reduce the bar phenomenon, even after the thin slice fracture and directly clashing into DLSE surface 50.Embodiment 2
Embodiment 2 is similar to embodiment 1, and different is, the solid content of fluorine chemistry oligopolymer in ethyl acetate is 1%, rather than 10%.Similar with this composition resulting results of property that has changed to the composition of embodiment 1.Embodiment 3
Embodiment 3 is similar to embodiment 1, and different is, the solid content of fluorine chemistry oligopolymer in ethyl acetate is 5%, rather than 10%.Similar with this composition resulting results of property that has changed to the composition of embodiment 1.Embodiment 4
Embodiment 4 is similar to embodiment 1, and different is, the solid content of fluorine chemistry oligopolymer in ethyl acetate is 20%, rather than 10%.Similar with this composition resulting results of property that has changed to the composition of embodiment 1.Comparative example: teflon coating
Polytetrafluoroethylene (PTFE) coating (silane coupling agent and topcoating) is applied on the part of the die head (comprising die head top and die holder).Use and the essentially identical manufacture method of previous embodiment, comprise sandblasting is carried out on the part of the die head surface.The preparation method of silane coupling agent is to stir silane coupling agent and also filter with 150 order stainless steel metal silk screens or cheese cloth.With silane coupling agent being applied to the part of the die head surface with the described identical method of previous embodiment.The dried thickness of required coating of silane coupling agent is 0.001 inch (25.4 microns).Silane coupling agent at air drying 1-5 minute, is placed on then and slowly was heated to 400-450 °F (204-232 ℃) in the baking oven also lasting 10 minutes.Then the power supply of baking oven is turned off, allowed part of the die head be cooled to about the room temperature.Used silane coupling agent is the antiseized silane coupling agent of green tetrafluoroethylene (DuPont company product) of 856-204 series.Die cleaned parts and de-oiling fat then.
Then prepare PTFE topcoating (856-200 series varnish topcoating, DuPont company product), its method is, stirs lightly 15-30 minute, filters with 100 order stainless (steel) wires.Part of the die head is preheated to 120-140 °F (48.8-60.0 ℃), allows topcoating leave standstill at room temperature.Then in 40-50 pound/inch
2(2.76-3.45 * 10
2KPa) topcoating is sprayed on the surface of primary coat.Top coat maximum dry thickness is 0.0`01 inch (25.4 microns).
The part of the die head that surface coated is crossed is put back in the baking oven then, slowly is heated to 575 °F (301.7 ℃) and continues 60 minutes.Allow part of the die head slowly cool at least 150 °F (65.6 ℃) again.Then, repeat surface coated and heating, cooling step, until the dried thickness of final top coat (that is, repeating 3-5 time at least) that obtains 0.004-0.006 inch (101.6-152.4 micron).
This coating is not carried out contact angle determination.But expect that its measurement result is similar to the contact angle of pure tetrafluoroethylene.When making water, the contact angle of pure tetrafluoroethylene is 84.0 degree; When using the aqueous solution of 6.4%MEK, the contact angle of pure tetrafluoroethylene is 36.9 degree; When using 100% MEK, the contact angle of pure tetrafluoroethylene is 23.2 degree.
According to the disclosed content in front, it is possible under the situation that does not depart from the determined the spirit and scope of the invention of claims the present invention being made rational modifications and variations.
Claims (10)
1. macromolecular compound, fluorinated oligopolymer part, this fluorinated oligomeric thing partly contain fluoro aliphatic series side group, organic solubilized side group and with the side group of epoxy-silane reaction.
2. macromolecular compound as claimed in claim 1, wherein, the fluorinated oligomeric thing partly contains an aliphatic main chain, is connecting following groups on this main chain:
(ⅰ) has the fluoro aliphatic group of perfluorination end group;
(ⅱ) contain the organic solubilized group that many carbon atoms also can at random contain the Sauerstoffatom of one or more links;
(ⅲ) can with the organo-functional group of epoxy-silane reaction, each fluoro aliphatic group, organic solubilized group and can be connected independently on the aliphatic main chain by covalent linkage, heteroatoms or organic linking group with the organo-functional group of epoxy-silane reaction.
3. macromolecular compound as claimed in claim 1, wherein, fluoro aliphatic series oligopolymer part is represented with following formula:
In the formula, R
1, R
2And R
3Represent the polymerized unit that obtains by fluorinated monomer, two functional monomers and solubilising monomer respectively and form aliphatic main chain jointly;
Each Q represents covalent linkage, heteroatoms or organic linking group independently;
Rf represents to contain the fluoro aliphatic group of perfluorination end group;
Rb represent can with the group of epoxy-silane reaction;
Rs represents to contain the organic solubilized group that many carbon atoms also can at random contain the Sauerstoffatom of one or more links;
A, b, c and d are that to make this compound be the integer of oligopolymer;
Epoxy-silane is represented with following formula
Or
In the formula, m and n are 1 to 4 integers;
R is that carbon atom is at the aliphatic group below 10; Carbon atom is at the acyl group below 10; Or formula (CH
2CH
2O)
jThe group of Z, wherein j is at least 1 integer; Z is that carbon atom is at the aliphatic group below 10.
4. composition as claimed in claim 1, wherein, the fluorinated oligomeric thing partly contains about 2-25 fluoro aliphatic group.
5. composition as claimed in claim 1, wherein, the fluorinated oligomeric thing partly contains many solubilizing groups.
6. composition as claimed in claim 1, wherein, solubilizing group contains about 8-50 carbon atom, is straight chain, side chain, ring-type or their combination.
7. composition as claimed in claim 1 wherein, solubilizing group and fluorinated oligomeric thing side joint, links with the fluorinated oligomeric thing or the two mixes.
8. prepare the method for compositions of claim 1, it may further comprise the steps:
(ⅰ) in inert solvent, the monomer of under the existence of chain-transfer agent and radical initiator following formula being represented mixes:
Rf-Q-CR
4H=CH
2
Rs-Q-CR
4H=CH
2
Rb-Q-CR
4H=CH
2
Rf represents to contain the fluoro aliphatic group of perfluorination end group;
Rs represents to contain the organic solubilized group that many carbon atoms also can at random contain the Sauerstoffatom of one or more links;
Rb represent can with the group of epoxy-silane reaction;
Each R
4Expression hydrogen, halogen or methyl;
Each Q represents covalent linkage, heteroatoms or organic linking group independently;
(ⅱ) make above-mentioned monomer reaction, form the composition that comprises one or more oligopolymer, these oligopolymer contain the part that useful following formula is represented:
In the formula, Q, Rf, Rs, Rb, R
4Definition the same, a, b, c and d are that to make this compound be the integer of oligopolymer;
(ⅲ) intermediate that will obtain by step (ⅱ) further with epoxy-polymerizable silane.
9. make liquid application device liquid of appearance when will use with the macromolecular compound of claim 1 and play the method that fringe phenomena is reduced to a minimum, it may further comprise the steps:
Bottom-coating is applied in the part that apparatus for coating contacts with liquid;
Undercoat is solidified, form the surface of primary coat;
Macromolecular compound is applied in the surface of primary coat;
Macromolecular compound is carried out radiation curing, form the low surface energy surface.
10. method as claimed in claim 9, this method is further comprising the steps of:
The part of bottom-coating to be applied in the apparatus for coating is done rough;
The part that has applied bottom-coating in the apparatus for coating is done rough;
After applying the macromolecular compound step, apparatus for coating is heated.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/659,053 US5998549A (en) | 1996-05-31 | 1996-05-31 | Durable, low surface energy compounds and articles, apparatuses, and methods for using the same |
| US08/659,053 | 1996-05-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1220673A true CN1220673A (en) | 1999-06-23 |
Family
ID=24643839
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97195111A Pending CN1220673A (en) | 1996-05-31 | 1997-04-23 | Durable, low surface energy compounds and articles, apparatuses, and methods for using the same |
Country Status (11)
| Country | Link |
|---|---|
| US (2) | US5998549A (en) |
| EP (1) | EP0902797B1 (en) |
| JP (2) | JP2000511955A (en) |
| KR (1) | KR20000016057A (en) |
| CN (1) | CN1220673A (en) |
| AR (1) | AR007344A1 (en) |
| AU (1) | AU2925297A (en) |
| BR (1) | BR9709283A (en) |
| CA (1) | CA2255583A1 (en) |
| DE (1) | DE69703547T2 (en) |
| WO (1) | WO1997046598A1 (en) |
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|---|---|---|---|---|
| CN105026446A (en) * | 2012-11-13 | 2015-11-04 | 3M创新有限公司 | Curable antifouling composition, method of use, and articles |
| CN110880550A (en) * | 2018-09-05 | 2020-03-13 | 杭州纤纳光电科技有限公司 | Coating equipment and method for precursor solution containing surfactant |
| CN115175772A (en) * | 2020-03-11 | 2022-10-11 | 富士胶片株式会社 | Die head |
| CN115190823A (en) * | 2020-03-05 | 2022-10-14 | 富士胶片株式会社 | Die head |
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| US6495624B1 (en) | 1997-02-03 | 2002-12-17 | Cytonix Corporation | Hydrophobic coating compositions, articles coated with said compositions, and processes for manufacturing same |
| US6156389A (en) * | 1997-02-03 | 2000-12-05 | Cytonix Corporation | Hydrophobic coating compositions, articles coated with said compositions, and processes for manufacturing same |
| US8653213B2 (en) | 1997-02-03 | 2014-02-18 | Cytonix, Llc | Hydrophobic coating compositions and articles coated with said compositions |
| US6391807B1 (en) * | 1999-09-24 | 2002-05-21 | 3M Innovative Properties Company | Polymer composition containing a fluorochemical oligomer |
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| ATE432298T1 (en) * | 2001-01-19 | 2009-06-15 | 3M Innovative Properties Co | FLUOROVINYL LIGOMER COMPONENT WITH SILANE GROUPS, LIQUID COMPOSITIONS THEREOF AND COATING METHOD |
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- 1996-05-31 US US08/659,053 patent/US5998549A/en not_active Expired - Fee Related
-
1997
- 1997-04-23 DE DE69703547T patent/DE69703547T2/en not_active Expired - Fee Related
- 1997-04-23 CA CA002255583A patent/CA2255583A1/en not_active Abandoned
- 1997-04-23 JP JP10500565A patent/JP2000511955A/en not_active Ceased
- 1997-04-23 CN CN97195111A patent/CN1220673A/en active Pending
- 1997-04-23 EP EP97923453A patent/EP0902797B1/en not_active Expired - Lifetime
- 1997-04-23 AU AU29252/97A patent/AU2925297A/en not_active Abandoned
- 1997-04-23 KR KR1019980709624A patent/KR20000016057A/en not_active Application Discontinuation
- 1997-04-23 WO PCT/US1997/006882 patent/WO1997046598A1/en not_active Application Discontinuation
- 1997-04-23 BR BR9709283A patent/BR9709283A/en not_active IP Right Cessation
- 1997-05-30 AR ARP970102327A patent/AR007344A1/en not_active Application Discontinuation
-
1999
- 1999-11-16 US US09/442,166 patent/US6231929B1/en not_active Expired - Lifetime
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2007
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105026446A (en) * | 2012-11-13 | 2015-11-04 | 3M创新有限公司 | Curable antifouling composition, method of use, and articles |
| US10947396B2 (en) | 2012-11-13 | 2021-03-16 | 3M Innovative Properties Company | Curable antifouling composition, method of use, and articles |
| CN110880550A (en) * | 2018-09-05 | 2020-03-13 | 杭州纤纳光电科技有限公司 | Coating equipment and method for precursor solution containing surfactant |
| CN115190823A (en) * | 2020-03-05 | 2022-10-14 | 富士胶片株式会社 | Die head |
| CN115175772A (en) * | 2020-03-11 | 2022-10-11 | 富士胶片株式会社 | Die head |
Also Published As
| Publication number | Publication date |
|---|---|
| US5998549A (en) | 1999-12-07 |
| DE69703547D1 (en) | 2000-12-21 |
| BR9709283A (en) | 1999-08-10 |
| EP0902797B1 (en) | 2000-11-15 |
| EP0902797A1 (en) | 1999-03-24 |
| JP2007302899A (en) | 2007-11-22 |
| DE69703547T2 (en) | 2001-06-21 |
| KR20000016057A (en) | 2000-03-25 |
| WO1997046598A1 (en) | 1997-12-11 |
| CA2255583A1 (en) | 1997-12-11 |
| AU2925297A (en) | 1998-01-05 |
| AR007344A1 (en) | 1999-10-27 |
| JP2000511955A (en) | 2000-09-12 |
| US6231929B1 (en) | 2001-05-15 |
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